Chennai Petroleum Corporation Limited

(A group company of IndianOil)

HYDROCRACKER OPERATION
Presented by
V.Vasant Kumar
Chief Manager- Process Engineering
RESOT Centre
17
th
March 2011
Topics
Topics
for discussion
for discussion
What is a Hydro-cracker?
What Does a Hydro-cracker Do?
Hydro-cracker Merits &Demerits.
History of Hydro-cracking.
Chemistry of Hydro-cracking.
Process Configurations.
Topics for discussion (
Topics for discussion (
Contd.)
Contd.)
Process descriptions- General
Process Variables
Emergency handling
Modifications& operational Improvement
done in CPCL OHCU.
Case study CPCL OHCU.
Hydro-cracking Licensors
Process Units
Process Units
Unit Licensor Capacity
CDU / VDU EIL 3.0 MMTPA
Visbreaker Lummus 1.15 MMTPA
Netherlands
Hydrocracker Chevron Lummus 1.65 MMTPA
Global,USA
CRU Axens, France 225,000 TPA
Hydrogen Technip Benelux 45,000 TPA(56,000)
Netherlands
Process Units
Process Units
Unit Licensor Capacity
LPG & UOP, USA 42,000 TPA
Kero Merox 600,000 TPA
Sulphur Recovery EIL / 180 TPD
Delta Hudson, Canada
Amine Regeneration EIL 330 MT/hr
Amine Treating :
a) Fuel gas treating EIL 35,000 TPA
b) LPG treating EIL 60,000 TPA
Sour Water Stripper EIL 60 TPH
What is a Hydrocracker?
What is a Hydrocracker?
What is a Hydrocracker?
It is a catalytic process for treating and cracking of
H-C feed to lighter products under the condition of
high hydrogen partial pressure and high temperature
in the presence of a catalyst.
What does a Hydrocracker do?
What does a Hydrocracker do?
Removes Metals (HDM) 100%
Removes Olefins 100%
Removes Sulfur (HDS) 100%
Removes Nitrogen (HDN) 100%
Saturates Aromatics (HAD) 50-95%
Convert Feed to Products 40-100%
H2 Consumption 170-422 Nm3/m3
Operating Pressure 70-210 kg/cm2G
Operating Temperature 315-430C

Removes Metals (HDM)

Removes Metals (HDM)
100%
100%

Removes Olefins
Removes Olefins
100%
100%

Removes Sulfur (HDS)

Removes Sulfur (HDS)
100%
100%

Removes Nitrogen (HDN)

Removes Nitrogen (HDN)
100%
100%

Saturates Aromatics (HAD)

Saturates Aromatics (HAD)
50
50
-
-
95%
95%

Convert Feed to Products

Convert Feed to Products
40
40
-
-
100%
100%

H2 Consumption
H2 Consumption
170
170
-
-
422 Nm3/m3
422 Nm3/m3

Operating Pressure
Operating Pressure
70
70
-
-
210 kg/cm2G
210 kg/cm2G

Operating Temperature
Operating Temperature
315
315
-
-
430
430

C
C
HYDROCRACKER MERITS &
HYDROCRACKER MERITS &
DEMERITS
DEMERITS
Merits:
i) upgrades heavier fraction of feed to superior quality products.
1. LN has RON, 78-85 - blending stock for the MS pool.
2. HN is excellent feed to reformer. Yields high RON, MS.
3. Jet fuel / SK low in aromatics & has high smoke point.
4. Diesel - high cetane No, low aromatics, sulfur content
5. Bottom products UCO Good feed to FCCU and LUBE
plant.
ii) Environmental regulations have imposed limits on the
aromatic and sulfur content of the diesel in order to reduce
emissions of carcinogens and sulfur oxides into the
atmosphere.
iii) More favorable for production of middle distillates when
compared to a FCC unit.
HYDRO
HYDRO
-
-
CRACKER MERITS &
CRACKER MERITS &
DEMERITS
DEMERITS
Demerits:
High investment cost.
Frequent mechanical problems with
equipments.
High energy consumption.(H2 requirement)
NOTE: With the catalyst development, utilization of
suitable metallurgy & experience gained,
Hydro-cracking has become a very reliable
process world-wide.
History of Hydro
History of Hydro
-
-
cracking
cracking
Early Hydro-cracking (liquid fuel from Coal):
Used Iron-Based Catalysts
Very High Pressures (352 kg/cm
2
G), 426C
Temperature.
Used by Germany in WW-II.
High Gas Make, Low Octane Naphtha, Poor
Quality Diesel (High in Aromatics)
History of Hydro
History of Hydro
-
-
cracking (contd.)
cracking (contd.)
First Modern Hydro-cracking
1959: Chevron Demonstrates Modern High Pressure
Process in Richmond Refinery-iso-cracking.
Union Oil Co Unicracking.
UOP lomax hydro-cracking process.
Employed Amorphous Silica-Alumina Catalysts.
Rapid growth of hydro-cracking after development of
new, Zeolite based hydro-cracking.
1962: Chevron Starts-Up the First Hydro-cracker in
the Then Sohio Refinery in Toledo, Ohio
1966: Chevrons Richmond Hydro-processing
Complex Starts-Up.
First Modern Hydro-cracking
1959: Chevron Demonstrates Modern High Pressure
Process in Richmond Refinery-iso-cracking.
Union Oil Co Unicracking.
UOP lomax hydro-cracking process.
Employed Amorphous Silica-Alumina Catalysts.
Rapid growth of hydro-cracking after development of
new, Zeolite based hydro-cracking.
1962: Chevron Starts-Up the First Hydro-cracker in
the Then Sohio Refinery in Toledo, Ohio
1966: Chevrons Richmond Hydro-processing
Complex Starts-Up.
History of Hydro
History of Hydro
-
-
cracking (contd)
cracking (contd)
State-of-the-Art Hydrocracking
1. Zeolitic Catalysts.
2. Lower Pressures, 70 200 kg/cm2G.
3. Moderate Temperatures 340 - 410C.
State-of-the-Art Hydrocracking
1. Zeolitic Catalysts.
2. Lower Pressures, 70 200 kg/cm2G.
3. Moderate Temperatures 340 - 410C.
Hydrocracking Licensors
Hydrocracking Licensors
Until Early 1990s, the Market (~120 HCRs) Was
Divided Roughly 1/3 Each Between UOP, Unocal
and Chevron.
In 1995, UOP Bought Unocal Technology, and
Now Have 2/3 of the Worlds HCRs.
Other Licensors (Minor Players).
IFP (Subsidized by French Government)
MAKFina (Mainly Compete in Mild HCR)
Shell Global (Several Captive Shell Units,
Criterion Cats)
Until Early 1990s, the Market (~120 HCRs) Was
Divided Roughly 1/3 Each Between UOP, Unocal
and Chevron.
In 1995, UOP Bought Unocal Technology, and
Now Have 2/3 of the Worlds HCRs.
Other Licensors (Minor Players).
IFP (Subsidized by French Government)
MAKFina (Mainly Compete in Mild HCR)
Shell Global (Several Captive Shell Units,
Criterion Cats)
Chemistry of
Chemistry of
Hydro
Hydro
-
-
cracking
cracking
Chemistry of Hydrocracking
Chemistry of Hydrocracking
Typical Hydro-processing & Hydro-cracking
Reactions:
1. De-metallization.
2. De-sulphurization.
3. Denitrification.
4. Olefin Saturation.
5. Aromatics Saturation
6. Hydro-Cracking
7. Sulphiding
8. De-methalization - Thermalcracking
9. Heat Release
Desulfurization reactions convert thiols or thiophenes to
straight-chain or branched paraffins and H2S. The heat of
reaction for desulfurization is about 560 kcal/Nm3 (60 Btu/SCF)
of hydrogen consumed.
R C CH
CH HC
S
+ 4H
2
Catalyst CH
3
CHCH
2
CH
3
Branched Paraffin
Thiophene
R
R
CH SH
R
+ H
2
Catalyst
Thiol
R
CH
2
R
Straight-Chain
Paraffin
+
H
2
S
+
H
2
S
Desulphurisation Reaction
Desulphurisation Reaction
RCH2 CH2 CH2 NH2 + H2 RCH2 CH2 CH3 + NH3
CATALYST
AMINE PARAFFIN AMMONIA
Typical hydrotreating reactions with nitrogen
compounds include hydrogenation of pyridines to form
paraffins and ammonia, quinolines to form aromatics
and ammonia, and pyrroles to form paraffins and
ammonia. The heat of reaction of the denitrification
reactions is about 660 kcal/Nm3 (70 Btu/SCF) of
hydrogen consumed.
R-CH2CH =CH2 + H2
RCH2CH2CH3
CATALYST
OLEFIN PARAFFIN
Hydrogenation of olefins is one of the most rapid of the
reactions taking place. All olefins are saturated very
early. The heat of reaction for these reactions is about
1320 kcal/Nm3 (140 Btu/SCF) of hydrogen consumed.
Because the olefin content of the Hydrocracker feed is
significant and because the saturation reactions are
rapid and release a large quantity of heat.
Olefins saturation
H
H
H
H H
\ /
R C==== C-H
\\ //
C---------C
/ \
H H
+ 3H2
C--------C
/ \
C ----------C
\ /
C --------- C
/ \ / \
H H H H
R
H
H H
H
AROMATIC
NAPHTHENE
Hydrogenated to naphthenes heat of reactions vary from about 380-
750 kcal/Nm3 (40-80 Btu/SCF) of hydrogen consumed depending
on the type of aromatic being saturated. In general, higher
pressures and lower temperatures result in a greater
degree of aromatic saturation
LARGE HC MOLECULES -------> SMALLER MOLECULES
Paraffin of paraffin of
high carbon no. Catalyst (Ni3S2) less carbon no.
CnH
2n+2
+ (x-1) H
2
x C
n/x
H
2n/x +2
+ Heat
Where x = no. of fragments ( low carbon no. Paraffin molecules),
Cracked from the high carbon no. Paraffin molecule.
The heat release from the hydro-cracking reactions
contribute appreciably to the total heat requirement.
H
2
+RCH
2
CH
2
CH
2
CH
3
---------> CH
3
CH
2
CH
3
+RCH
3
Catalyst
Chemistry of Hydrocracking
Chemistry of Hydrocracking
Hydro-Cracking Reactions:
Large Side Chains Easily Removed From
Rings
Saturated Rings Crack Easily.
Paraffins Hard to crack.
Paraffin Products Are Highly Isomerized.
Hydro-Cracking Reactions:
Large Side Chains Easily Removed From
Rings
Saturated Rings Crack Easily.
Paraffins Hard to crack.
Paraffin Products Are Highly Isomerized.
Chemistry of Hydro
Chemistry of Hydro
-
-
cracking
cracking
Hydro-Cracking Reactions (CON):
In the reactors, sulphur and nitrogen are removed from the
feedstock. In general, the carbon skeleton of the feed
molecule is not altered by heteroatom removal; however,
the boiling point of the molecule decreases by 27-54C for
sulphur compounds and up to 104C for nitrogen
compounds. Alkyl aromatics also react in the reaction stage
to give three types of products:
Aromatic- saturation to give a naphthene.
Aromatic- dealkylation to give a paraffin and
aromatic- piece.
Aromatic- condensation to give a polycyclic aromatic.
NOTE:The amounts of each type of product depend on
processing conditions (temperature, catalyst, and hydrogen
partial pressure) and feed composition.
Chemistry of Hydrocracking
Chemistry of Hydrocracking
Other Important Reactions
Thermal Hydrocracking or De-methylation
Undesirable Side Reaction Occurring at >465C
Can Occur at Lower Temperatures With Reduced,
Unsulfided Metals
Produces Light Gases, Mainly Methane
High H2 Consumption, Uncontrollable Heat
Release
Other Important Reactions
Thermal Hydrocracking or De-methylation
Undesirable Side Reaction Occurring at >465C
Can Occur at Lower Temperatures With Reduced,
Unsulfided Metals
Produces Light Gases, Mainly Methane
High H2 Consumption, Uncontrollable Heat
Release
Catalyst Sulfiding
Catalyst Sulfiding
Fresh catalyst as well as regenerated catalyst need to be
sulfided so that the optimum catalyst stability and activity
can be obtained before oil feed is introduced.
The sulfiding process consists of catalyst pretreatment with a
sulfiding agent in the presence of hydrogen. When heated
and passed over the catalyst, the sulfiding agent breaks down
into H2S which reacts with the metal oxides on the catalyst,
thereby generating active metal sites (metal sulfides).
The reactions taking place during sulfiding are as follows:
(1) Cracking of DMDS (The Sulfiding Agent)
CH
3
-S-S-CH
3
+ 3H
2
2CH
4
+ 2H
2
S
This occurs at temperatures between 218232C for
DMDS.
(2) Conversion of metal oxide to metal sulfide
2H
2
S + 3NiO + H
2
Ni
3
S
2
+ 3H
2
O
Heat Release/H
Heat Release/H
2
2
Consumption
Consumption
From Hydro
From Hydro
-
-
crackers
crackers
Reaction H
2
Consumption
Heat Release,
(Kcal/ Nm3
H
2
)
HDS 3 mols H
2
/mol S
(17-25 Nm
3
/m
3
Per 1% S Removed)
565
HDN ~5 mols H
2
/mol N
(5-7 Nm
3
/m
3
Per 1000 ppm N Removed)
610-705
Olefin
Saturation
~1 mol H
2
/C=C Bond 1200-1500
HDA ~ 3 mols H
2
/Ring Saturated
(2-5 Nm
3
/m
3
Per 1% Rings Reduced)
660-800
Cracking 2-5 Nm
3
/m
3
Per 1 LV% Conv. 470-565
Process Configurations
Process Configurations
Process Configurations
Process Configurations
Process Configurations
Single Stage - for 100% conversion of feed
into products.
Single stage - Once-Through operation
CPCLs design configuration
Single Stage Recycle
- CPCLs initial operation configuration
Two Stage Recycle

Single Stage
Single Stage
-
-
for 100% conversion of feed
for 100% conversion of feed
into products.
into products.

Single stage
Single stage
-
-
Once
Once
-
-
Through operation
Through operation

CPCL
CPCL

s design configuration
s design configuration

Single Stage Recycle

Single Stage Recycle
-
-
CPCL
CPCL

s initial operation configuration

s initial operation configuration

Two Stage Recycle

Two Stage Recycle
Features
Low Investment
Low Hydrogen Consumption
Very Flexible Plant, Handles a Variety of
Feeds
Can Handle High End Point, High N
Feeds
Pretreats VGO for FCC Feed
Produces High VI Lube Base Stocks
Features
Low Investment
Low Hydrogen Consumption
Very Flexible Plant, Handles a Variety of
Feeds
Can Handle High End Point, High N
Feeds
Pretreats VGO for FCC Feed
Produces High VI Lube Base Stocks
Single-Stage Once-Through
(SSOT) Hydrocracking
Single
Single
-
-
Stage Once
Stage Once
-
-
Through
Through
(SSOT) Hydrocracking
(SSOT) Hydrocracking
Single Stage (SSOT)
Single Stage (SSOT)
Single Stage (SSOT)
CPCL SSOT YIELDS
CPCL SSOT YIELDS
Yields, Wt % SOR EOR
C
1
& C
2
C
3
s
C
4
s
Light Naphtha
0.64
0.67
1.46
3.40
1.11
1.00
2.31
3.60
Heavy Naphtha 5.10 5.10
Kerosene
Diesel
Bottoms
C5+,
23.69
21.75
42.43
96.37
23.60
20.02
42.42
94.75
CPCL SSOT YIELDS
Integration of Hydrocracker Unit with
Integration of Hydrocracker Unit with
the existing FCCU
the existing FCCU
The superior quality of unconverted oil from HCU bottom (sulphur content < 50 ppmw,
N2 content < 1 ppm and metals < 0.1 ppm) is routed to FCCU as feed to derive the
following benefits :
Improved yield pattern :
Previous Feed (wt.%) Present Feed (wt.%)
(Ref-II VGO) (UCO from HCU)
Gas 2.6 2.5
LPG 13.0 32.0
Gasoline 27.4 49.0
TCO 45.9 10.0
CLO 5.2 2.0
Coke 5.9 4.5
Advantages :
1. Substantial increase in LPG and Gasoline yields.
2. Reduction in CLO and Coke yields.
3. Better quality products with very low sulphur content (MS S <10 ppm,
RON 91 and TCO S content <100 ppm).
4. Reduction in SO2 emission due to lower sulphur content in feed.
Features: Relative to SSOT
Can Achieve Almost Full Conversion (97%)
Moderate Investment
High Quality Products
High Hydrogen Consumption
Features: Relative to SSOT
Can Achieve Almost Full Conversion (97%)
Moderate Investment
High Quality Products
High Hydrogen Consumption
Single-Stage Recycle (SSREC)
Hydrocracking
Single
Single
-
-
Stage Recycle (SSREC)
Stage Recycle (SSREC)
Hydrocracking
Hydrocracking
Make Make- -Up Up
Hydrogen Hydrogen
Fresh Fresh
Feed Feed
First First - -Stage Stage
Product Product
Recycle Recycle
Gas Gas
Make Make- -Up Hydrogen Up Hydrogen
Recycle Recycle
Gas Gas
Second Second- -Stage Product Stage Product
Light Light
Naphtha Naphtha
Heavy Heavy
Naphtha Naphtha
Kerosene Kerosene
Diesel Diesel
Product Product
Gas Gas
Maximum Liquid Yield and Highest Quality
Maximum Liquid Yield and Highest Quality
Two Stage Recycle (TSR)
Two Stage Recycle (TSR)
Two Stage Recycle (TSR)
Single-Stage, Once-Through-Liquid (SSOT)
Low Conversion (35-70%)
Minimal Quality Products (UCO to FCC U as Feed)
Relatively Low Investment
Single-Stage Recycle (SSREC)
High Conversion (90+%)
High Quality Products
Moderate Investment With Easy Feeds
Two-Stage Recycle (TSR)
Full Conversion
Very High Quality Products
Moderate Investment With Difficult Feeds
Single-Stage, Once-Through-Liquid (SSOT)
Low Conversion (35-70%)
Minimal Quality Products (UCO to FCC U as Feed)
Relatively Low Investment
Single-Stage Recycle (SSREC)
High Conversion (90+%)
High Quality Products
Moderate Investment With Easy Feeds
Two-Stage Recycle (TSR)
Full Conversion
Very High Quality Products
Moderate Investment With Difficult Feeds
Hydrocracking Configurations
Summary
Hydrocracking Configurations
Hydrocracking Configurations
Summary
Summary
Product Qualities
Product Qualities
Single vs Two stage hydro
Single vs Two stage hydro
-
-
cracker
cracker
Product Properties VGO HDT SSOT SSREC TSR
Jet Smoke Point, mm 10-15 15-20 20-25 25-30
Heavy Diesel Cetane
Number
50 50-55 60-65 65-70
Feed & products
Feed & products
Straight run gas oil.
Vacuum Gas Oil (LVGO & HVGO ).
De-asphalted Oil (DAO).
FCCU cycle oil.
Cocker gas oil.
Distillates.
Extracts.
Straight run gas oil.
Vacuum Gas Oil (LVGO & HVGO ).
De-asphalted Oil (DAO).
FCCU cycle oil.
Cocker gas oil.
Distillates.
Extracts.
Typical Feed stocks
Typical Feed stocks
Typical Feed stocks
HYDROCRACKER FEED STREAMS
HYDROCRACKER FEED STREAMS
-
-
CPCL
CPCL
HVGO Stream from Ref-II and Ref-III
DAO
dist 95%@585C, vis 33 36cst @100C, asp < 100 ppmw
Foots Oil
CCR 0.4%wt, Asp 40-50 ppmw, Metals* 3 ppmw
Slack wax
CCR - <0.1% wt, Asp 90 ppmw, Metals 1 ppmw
Lube distillate & Lube slop
-CCR 0.6% wt, Asp 70 ppmw, Metals 3.5 ppmw
VB-VGO
(* Metals = Ni+V+Fe+Na)
Products from hydro
Products from hydro
-
-
cracker
cracker
HYDROCRACKER UNIT PRIMARY PRODUCTS:
1. Aviation Turbine Fuel/Superior Kerosene .
2. Diesel
3. LPG
4. Light Naphtha to H2 Unit or gasoline/ LN pool.
5. Heavy Naphtha to Reformer Feed Or diesel pool.
6. Unconverted Oil to FCC Feed or Storage
7. CLPS Off gas to Hydrogen PSA Unit/Fuel Gas
8. Sponge Oil Absorber Sweet Off gas to Fuel Gas
HYDROCRACKER UNIT BY- PRODUCTS:
1. Filter Back flush to Fuel Oil/ FCC Feed
2. Sour Water to Sour Water Stripper
3. Spent Caustic Solution to Spent Caustic System
4. Blow down from Steam Generators to Storm Water Sewer
CRACKING REACTIONS ARE PERMITTED BY ACID SITES
HYDROGENATION BY METAL SITES
ACID FUNCTION IS SUPPLIED BY CATALYSTS BASES AND
THESE ARE AMORPHOUS SILICA,ALUMINA OR ZEOLITE
CATALYST BASE DEPENDS ON THE TYPE OF PRODUCT
REQUIRED.
METALS SUCH ASMOLYBDENUM, TUNGSTEN, COBALT,
NICKEL, PLATINUM, PALIDIUM ARE DISPERSED ON THE
CATALYST BASE.
NITROGEN IN FEED GETS IS CONVERTED TO AMMONIA
THROUGH REACTIONS AND NH3 SO FORMED PARTIALLY
NEUTRALISES THE ACIDIC SITES THUS REDUCING
CAT.ACTIVITY.
Catalyst
Catalyst
-
-
CPCL Hydrocracker
CPCL Hydrocracker
Total Requirements for
Catalyst Type Shape
Loaded
Densities,
kg/m
3
Diameter,
mm Reactors 207-R1, 207-R2
Demetallization
and Grading
Sphere 913 ~4.23 16,130 37.3 203
Hydrotreating 977
ICR 134SAQ Asym Quad 2.82 x 2.31 75,022 82.2 551
Hydrocracking
ICR 126 Cylinder 951 2.54 113,348 116 667
ICR 126L Cylinder 977 1.59 12,525 12.8 494
ICR 126N Cylinder 896 2.12 69,547 73.1 438
Support 432
ICR 114ZF Trilobe 2,160 ~4.23 7,075 8 50
6/12/2006 mrb G2000829 Krishna 21
CONFIDENTIAL
Property of Chevron
To be Reproduced and Used only in
accordance with written permission of Chevron.
VOL
M3
VOL
%
CAT
TYPE
207 R1, Bed 1

207 R1, Bed 2
207 R1, Bed 3

207 R2, Bed 1
207 R2, Bed 2
37.3

52.5
29.6
30.1
86.0
12.8
11.6

16.3
9.2
9.4
26.8
4.0
ICR-122 ZSB, Demet

ICR-134 SAQ, HDT
ICR-134 SAQ, HDT
ICR-126 , HCR
ICR-126, HCR
ICR-126 N, HCR
73.1 22.7 ICR-126 L, HCR
Total 321.4 100.0
CPCL ACTIVE CATALYST LOADING
CPCL ACTIVE CATALYST LOADING
Function Catalyst
ICR122ZSB
De-metallization
Support
ICR 114ZF
ICR 134SAQ
Support
Hydro-treating
ICR 114ZF
ICR 134SAQ
Hydrocracking
Hydro-treating
ICR 126
Support
ICR 114ZF
13.1m3
82.2m3
1.6m3
46.7m3
Support Balls
1.6m3
37.3m3
207-R1 Catalyst System
207
207
-
-
R1 Catalyst System
R1 Catalyst System
207-R2 Catalyst System
207
207
-
-
R2 Catalyst System
R2 Catalyst System
1.6m3
69.4m
3
Function Catalyst
ICR 126
Support
Hydrocracking
Support
Hydrocracking
ICR 114ZF
ICR 126N/126L
ICR 114ZF
1.6m3
Support Balls
Regenerable
Carbon Deposits or Coke Caused by Adsorbed
Condensed Polycyclic Compounds
Adsorbed Organic Nitrogen Compounds Which Tie Up
Acid Sites, Thus Lowering Cracking Activity
Nonregenerable
Deposited Feed Metals - Ni, V, Si, Fe, As, Pb, P
Metals Tend to Deposit Near the Outer Edge of the
Catalyst and Plug the Catalyst Pores
Regenerable
Carbon Deposits or Coke Caused by Adsorbed
Condensed Polycyclic Compounds
Adsorbed Organic Nitrogen Compounds Which Tie Up
Acid Sites, Thus Lowering Cracking Activity
Nonregenerable
Deposited Feed Metals - Ni, V, Si, Fe, As, Pb, P
Metals Tend to Deposit Near the Outer Edge of the
Catalyst and Plug the Catalyst Pores
Catalyst Deactivation Caused
By Deposits and
Contaminants
Catalyst Deactivation Caused
Catalyst Deactivation Caused
By Deposits and
By Deposits and
Contaminants
Contaminants
Sulfur leaching.
Sulfur leaching.
Normally when H2 is circulated at higher
temperature over the sulphided catalysts the sulphur
will be converted to H2S and the metal sulphides will
be converted to metals, which will reduce the
activities. Fresh or regenerated catalyst will be in
metal oxide, during sulphiding this metal oxides will
become metal suphides. If leaching occur the metal
can not be sulphided again and will result in
reduction of active catalyst volume. In CPCL case,
licenser has noted operating at higher temperature
will effect no leaching. but in the case of hydro-
treaters there is a temperature limit above which we
can not circulate H2 with out oil.
Process description
Process description
Process description
Process description
The Hydro-cracker Unit consists of five sections:
1. Feed and Reaction Section
2. Recycle Gas Loop and Oil/Gas Separation Section
3. Fractionation Section
4. Light Ends Recovery Section
5. Make-Up Hydrogen Compression Section
VGO
feed
249.2
m
3
/hr.
Feed
preheating
and
filtration
Furnace
Product
stripper
Light end
recovery
section
Fractionator
Fuel gas (to header) 2147 nm
3
/hr.
Light Naphtha (to MS pool / HGU) 12.3 m
3
/hr.
Heavy Naphtha (to Diesel pool / CRU) 15.5 m
3
/hr.
Off-gas to PSA
(for
H
2
recovery)
LPG (to storage) 7.8 m
3
/hr.
Kerosene / ATF 67.2 m
3
/hr.
.
Diesel 59.8 m
3
/hr.
.
HP
gas separator
LP
gas separator
Recycle gas
compressor
(RGC)
Amine
treating
Recycle gas
2,10,489 nm
3
/ hr.
Furnace
UCO (to FCCU) 115.6 m
3
/hr.
.
Gas
Liquid hydrocarbon
Heavier
hydrocarbons
Lighter hydrocarbons
Lighter hydrocarbons
Make-up H
2
from HGU
360
0
C
Reactors
172.5 Kg/cm
2
378
0
C
Make-up H
2
compressor
Quench
H
2
Make-up H
2
68,370Nm
3
/ hr.
185 kg / cm
2
68,370 Nm
3
/ hr.
VGO feed
249.2 m
3
/hr.
Fuel gas
Feed
surge
drum
Feed pump
Fuel gas
and
Fuel oil
MPS
Kero./ ATF R/D
67.2 m /hr.
3
Kero. P/A
3
3
Diesel P/A
UCO R/D (to FCCU)
115.6 m /hr.
Diesel R/D
59.8 m /hr.
Fractionator
Off-gas to
sponge-oil absorber
and then to FG header
2147 nm
3
/hr.
CW
CW
LPG
to caustic treatment
and then to Sphere
7.8 m
3
/hr.
HN
(to Diesel pool /
HGU)
12.3 m
3
/hr.
LN
(to MS pool / HGU)
12.3 m
3
/hr.
Deethaniser
Naphtha splitter
Debutaniser
Lean
amine
Rich amine
to recovery
Quench
H
2
Reactors
207R-1 207R-2
Product
stripper
Reactor feed
furnace
C
H
P
S
C
L
P
S
recycle gas
2,10,489 nm
3
/hr
Fractionator
feed furnace
RGC
Amine
absorber
MUGC
H
2
from HGU
185 kg/cm
2
68,370 nm
3
/hr.
PDI
Feed filter
HPS
To amine absorber
& then to PSA
(for H
2
recovery)


Feed
preheat
Feed Filter System
Feed Filter System
The oil feed must be filtered to remove solids and
particulates which would otherwise lay down on the First
Reactor top bed catalyst, prematurely plugging the top
bed.
- Feed Filters, which remove solids and particulates
from the oil feed. (more than 20micron size
particles are trapped).
The preheated, combined oil feeds stream enter the feed
filters at 168C where most of the solids and particulates
are trapped and removed from the reactor oil feed
stream.
First and Second Reactors
First and Second Reactors
207R
207R
-
-
1 and 207R
1 and 207R
-
-
2
2
The purpose of the First and Second Reactors is to provide a
controlled environment for the hydro-cracking and hydro-
treating reactions to take place.
R1 and R2, reactors and their internals is to promote the
hydro-treating and hydro-cracking reactions at a controlled
rate. Temperature and good flow distribution in the reactors
are the key to controlling reaction rate and achieving good
catalyst utilization.
Hydro-treating and hydro-cracking reactions are exothermic
and higher temperatures lead to higher reaction rates. In
order to control this temperature rise and, likewise, the rate
of reaction, the catalyst is separated into three beds in the
first reactor and two beds in the second reactor.
Essential guidelines

Cold High Pressure Separator

Cold High Pressure Separator
(CHPS)
(CHPS)
Cold High Pressure Separator (CHPS), - Separates the reactor effluent
into hydrogen-rich vapor, water, and hydrocarbon liquid reaction
products.
The CHPS hydrogen-rich vapor steam (recycle gas) is sent to the high
pressure centrifugal separator to ensure no liquid entrainment.
Hydrocarbons make amine foam.
The relief valve for the high pressure loop is located on the CHPS. The
set pressure of this pilot-operated relief valve is 5% greater than the
normal operating pressure of the CHPS .
The CHPS temperature is controlled by adjusting the speed of the fans
operating in the reactor effluent air cooler. Lowering separator
temperature will:
1. Increase the recycle gas purity.
2. Lower the recycle compressor horsepower requirement.
3. Make separation of oil from water in the separator more
difficult.
HP H
HP H
2
2
S Absorber
S Absorber
HP H2S Absorber, 207-C4 - Scrubs H
2
S from the recycle gas stream by
contact with lean amine to help maintain high H2PP.
The normal operating temperature is 55-68C.
The high pressure absorber is designed and operated to keep hydrocarbon
from condensing into the amine. Vapor lines are heat traced and the
amine is kept 5C hotter than the vapor.
The temperature of the lean amine must be maintained 5C hotter than the
feed vapor temperature to prevent and condensation of the vapor on
contacting the lean amine. (This is critical in preventing foaming in the
absorber.)
A chopper valve will close on low-low flow (20%) to prevent backflow of
high pressure gas on loss of the lean amine charge pumps.
Recycle Gas Compressor
Recycle Gas Compressor
Recycle Gas Compressor - Supplies the
pressure to move the recycle gas through the
reactor system.
To maintain H2 partial pressure.
To remove the heat of reaction.
To improve oil/gas distribution.
To remove products from the reactors as
soon as they are formed to prevent
secondary cracking.
Cold Low Pressure Separator (CLPS)
Cold Low Pressure Separator (CLPS)
Cold Low Pressure Separator (CLPS), - Separates hydrogen-rich
vapor, hydrocarbon liquid, and water phases
Reactor effluent liquid from the CHPS is let down in
pressure through a level control valve and then flashed in
the CLPS. It is a SS clad carbon steel, vertical vessel with
internals designed to separate hydrogen-rich vapor,
hydrocarbon liquid, and water phases. The CLPS removes
water carried over in the CHPS liquid. The hydrocarbon
liquid is the product stripper feed.
CLPS Vapor H
CLPS Vapor H
2
2
S Absorber
S Absorber
It Scrubs H2S from the CLPS Vapor by
contact with lean amine prior to sending
the vapor to the PSA Unit for hydrogen
recovery.
It is a SS clad carbon steel vessel with a
single packed bed.
The normal operating temperature is
61C and pressure is 38kg/cm2g.
Fractionation Section
Fractionation Section
The purpose of the Fractionation Section is to
separate reaction section products into sour
gas, unstabilized naphtha, kerosene, diesel,
and fractionator bottoms.
The sour gas and unstabilized naphtha are
sent to the Light Ends Recovery Section.
The kerosene and jet are finished products
and are sent to storage or blending.
The fractionator bottoms are sent to the FCC
Unit or storage.
HSD
STRIPPER
SK
STRIPPER
Operating condition
Operating condition
Fresh Feed Rate, BPOD (112% of
Design)
Fresh Feed Rate, MM MTPA
LHSV, 1/Hr (Note 1)
Gross Conversion, Vol %
Total Catalyst Life, Yr
207-R1 207-R2
Reactor Pressure, kg/cm
2
(g)
SOR/EOR
Inlet 172.5/176.0 167.4/167.4
Outlet 169.0/169.0 163.9/163.9
Average Hydrogen Partial Pressure,
kg/cm
2
(a)
145 135
Reactor Temperature, C
SOR/EOR
Inlet 378/396 378/396
Outlet 411/429 411/429
Maximum 440 440
Gas to Oil Ratio at Reactor Inlet, Nm
3
/m
3
Number of Reactors 1 1
5 (With Regeneration)
845
37,400
1.85
0.8
54
MAKE-UP H2 PURITY 99.5%
CHEMICAL H2 CONSUMPTION 262nm3/m3 of feed
HYDROGEN BLEED nil
Process variables
Process variables
Process variables
Process variables
1. FEED EFFECTS.
2. HYDROGEN EFFECTS.
3. CATALYST EFFECTS.
1. Reactor temperature profile.
2. Catalyst Average Temperature.
4. REACTION SECTION OPERATING
EFFECTS.
5. FRACTIONATION AND LER OPERATION
EFFECTS.
Process variables
Process variables
-
-
Feed effects
Feed effects
FEED EFFECTS:
1. LIQUID HOURLY SPACE VELOCITY
(FEED RATE)
2. NITROGEN.
3. ASPHALTENES.
4. METALS
5. POLYCYCLIC AROMATICS
6. SULFUR
7. CHLORIDES
Process variables
Process variables
-
-
LHSV
LHSV
Liquid Hourly Space Velocity (LHSV)
Definition: The ratio of reactor feed rate
(m3/hr) to catalyst volume(m3).
Unit is inverse hours (1/hr)
) , (
) , ( * ) 234 . 0 (
3
Ft Volume Catalyst Active
BPOD Rate Feed Oil
LHSV =

Determinants
Active Catalyst Volume (Design Feature)
Feed Rate
Effects of Higher LHSV
Degrades Product Properties at Same Catalyst
Average Temperature (CAT).
Increase CAT to Maintain Product
Specifications .
Increased CAT Increases Coking .
Higher CAT Reduces Cycle Length .
LHSV Should be Optimized to Meet Product
Properties and Catalyst Life .
Determinants
Active Catalyst Volume (Design Feature)
Feed Rate
Effects of Higher LHSV
Degrades Product Properties at Same Catalyst
Average Temperature (CAT).
Increase CAT to Maintain Product
Specifications .
Increased CAT Increases Coking .
Higher CAT Reduces Cycle Length .
LHSV Should be Optimized to Meet Product
Properties and Catalyst Life .
Process variables- LHSV
Process variables
Process variables
-
-
LHSV
LHSV
Typical Nitrogen Levels Are <1100 ppm
Nitrogen is a Strong Poison for Acid Sites in HCR
Catalysts.It is a temporary catalyst poison.
It neutralise the active site.
Desorption rate is very slow. It will take several days to
desorb.
Higher N2 in feed requires higher CATs to achieve a
desired conversion this will result in Shorten the Cycle
Life.
Higher NH3 Levels Will need higher Water Wash Rates.
Typical Nitrogen Levels Are <1100 ppm
Nitrogen is a Strong Poison for Acid Sites in HCR
Catalysts.It is a temporary catalyst poison.
It neutralise the active site.
Desorption rate is very slow. It will take several days to
desorb.
Higher N2 in feed requires higher CATs to achieve a
desired conversion this will result in Shorten the Cycle
Life.
Higher NH3 Levels Will need higher Water Wash Rates.
Effect of Feed Nitrogen Content
Effect of Feed Nitrogen Content
Effect of Feed Nitrogen Content
Effect of Asphaltene in Feed
Effect of Asphaltene in Feed
Asphaltene content should be less than
100ppm.
Defficult to crack and saturate.
Polymerise on the catalyst surface as
carbonaceous deposits.
Note : Asphaltene content can be reduced by
proper operation of upsteam unit.
Effect of Metals in Feed
Effect of Metals in Feed
Ni, Va, Na, Ca & Mg -present in the feed. Limit is
1ppm (max).
Metels are too large to fit inside the catalyst pores.
Deposited on the catalyst and irreversibly destroy its
activity.
Fe not only deactivate the catalyst through pore
mouth plugging and cause pressure drop across the 1
st
bed of the 1
st
reactor.
Note : Metal content can be reduced by proper operation
of upsteam unit.
Effect of polycyclic aromatics
Effect of polycyclic aromatics
in Feed
in Feed
Polycyclic aromatics (PCA) Coke
precursors.
It is a large multi-ring aromatic compounds
tend to dehydrogenate on the catalyst,
ultimately forming coke.
Has a significant effect on catalyst activity
and fouling rate of down stream equipment.
Effect of Sulfur & chlorides in
Effect of Sulfur & chlorides in
Feed
Feed
Higher sulfur content would shorten the life of the
reactor and other critical equipment.
- It increases the H2S content of the recycle gas,
decrease H2 partial pressure and reduce the catalyst
performance.
Chloride limit is 1ppm(max).
The salt, Mgcl2 &Nacl, bulids up at the top of the 1
st
reactors.
Reactor pressure drop will increase. Limit the
feed rate and require a shut down.
It may cause fouling and stress corrosion cracking in
the feed/effluent exchanger.
Effect of Feed Boiling Range
Feed mixture is dependent on the crude oil used and the
operating conditions of the upstream units. The primary
function of the hydrocracker is to crack the large molecules
(VGO-sized) to smaller molecules (naphtha-, kerosene-,
diesel-sized).
As the feed boiling range increases, the levels of nitrogen,
polycyclic aromatics (PCA), asphaltenes, and metals
increase. A higher feed nitrogen level and higher PCA level
require a higher CAT. High PCA, asphaltene, and metal
levels increase the fouling rate of the catalyst. Therefore,
increasing the feed boiling range shortens the run span by
increasing both the required CAT and the fouling rate.
Catalyst poisons such as asphaltenes, metals, and nitrogen
increase exponentially with boiling point

Contaminant Source Effect on Isocracking
Catalyst
Ni + V High End Point Feed
1% Metals = 15F Activity Los
Si Silicone Antifoam Pore Mouth Plugging
Na Sodium Hydroxide
Desalting / Flooding
(poor de-salter operation)

1% = 15F Activity Loss
FeS
x
Corrosion Products Pore Mouth Plugging
As Arsenic in Crude
1% as = 50F Activity Loss
P Phosphoric Acid in Feed
1% P = 90F Activity Loss
Asphaltenes Residuum Higher Fouling Rate


Sources of Contaminants and
Their Effects
Sources of Contaminants and
Sources of Contaminants and
Their Effects
Their Effects
3/27/2003 mrb G2000829 Krishna 21
CONFIDENTIAL
Property of Chevron
To be Reproduced and Used only in
accordance with written permission of Chevron.
SR
VGO
VB
VGO
90% SRVGO
10% VB VGO
API
Sulfur, wt%
Nitrogen, ppm
Asphaltenes, ppm
CCR wt%
20.8
2.8
1000
100
0.6
20.7
5.0
2000
200
1.0
20.8
3.03
1102
110
0.64
Ni+V, ppm 1.0 9.0 1.8
Iron, ppm
D1160 EP, Deg C
0.0
585
5.0
500
0.5
585
CPCL FEED COMPOSITION
CPCL FEED COMPOSITION
FEED PROPERTIES
FEED PROPERTIES
-
-
CPCL
CPCL
-
-
OHCU
OHCU
Feed Specifications SR VGO VB VGO
CDU/VDU Bombay
High/Persian Gulf
Quality Specifications
Distillation, ASTM D 1160, C
Start 320 300
10% 380 324
30% 415 378
50% 440-460 402
70% 490 435
90% 540 473
End Point, Max. 585 500
API Gravity 20.8-34.8 20.7
Specific Gravity 0.825-0.929 0.93
Asphaltenes, Wt %, Max. 0.01 0.02
Iron, ppm 0 5
Nitrogen, ppmw 1000 2000
Sulfur, Wt % 2.8 5
Kinematic Viscosity at 50C, cSt 46.3
Kinematic Viscosity at 100C, cSt 9.6
Kinematic Viscosity at 200C, cSt 0.6-1.65
Kinematic Viscosity at 250C, cSt 0.4-1.1
CCR, Wt % 0.6 1
Nickel + Vanadium, ppm 1 9
Feedstock Sources Visbreaker
Unit
Products Specification
Products Specification
CPCL
CPCL
-
-
OHCU
OHCU
Product Inspections:
Cut Light
N hth
Heavy Naphtha Kerosene/ATF Diesel Bottoms
Cut Points, C C
5
-95 95130 130-260 260-370 370+
API Gravity 79 54 42.5 36.5 34.8
Density @15

C 670-675 763-768 812-817 820-870 850-855

ASTM,

C D 86 D 86 D 86 D 86 D 1160
ST 23 102 142 229 337
10 36 107 161 268 394
50 49 114 193 302 473
90 79 128 238 348 548
EP 91 147 266 376 562
Sulfur, ppm <5 <5 <50 (Max.)
Mercaptan Sulfur, ppm 10 (Max.) 10 (Max.)
Nitrogen, ppm <1 <1 <1 (Max.)
Paraffins, LV % (Estimated) 66 30
Naphthenes, LV %
(Estimated)
32 62
Aromatics, LV % (Estimated) 2 8 22
Flash Point,

C 38 (Min.) 35 (Min.)
Smoke Point, mm 21
Cetane Index (D 613) 55 (Min.)
Freeze Point,

C (-)51
Pour Point,

C 3 (Max.)
Viscosity @ 40

C, cSt 2 to 5
Viscosity @ 100C, cSt 4.2
Viscosity @ -20C, cSt 8
Water, ppm 500 (Max.)
Metals, ppm <0.1
Octane Number, Estimated
RONC/MONC 75/76 64/62
RVP, kg/cm
2
0.8 (Max.) 0.8 (Max.)
10 (Max.) 10 (Max.)
Process Variables
Process Variables

H
H
2
2
Effects
Effects
Hydrogen Partial Pressure.
Recycle gas purity
Mack-up H2 purity
Recycle gas rate (Gas/Oil Ratio)
Catalyst Temperature.
Catalyst life.
Process Variables
Process Variables
Reactor temperature profile.
Catalyst Average temperature.
Process variables
Process variables
-
-
Make up H
Make up H
2 2
Purity
Purity
Make-up hydrogen consists of a mixture of hydrogen
and methane. Methane is also produced in the
hydrocracking reaction. The hydrogen is consumed in
the hydrocracking reactions and lost.
To maintain the desired hydrogen partial pressure and
maintain the purity of the make-up hydrogen (99.5
mole%H2).
If the make-up hydrogen purity falls below the design
value, a bleed may be required to maintain an
acceptable hydrogen partial pressure.
H
2
partial press can be increased by
Increasing total system pressure (operate as close as the relief
valve set press located on the CHPS).
Increasing Make-Up Hydrogen Purity.
Increasing Recycle Gas Purity (Bleed, Treating)
Recycle Gas Rate.
Decreasing CHPS temperature.
Higher PH
2
Effects
Improves Product Properties (J et Smoke Point, Diesel
Cetane Number).
Increases Cycle Length.
H
2
partial press can be increased by
Increasing total system pressure (operate as close as the relief
valve set press located on the CHPS).
Increasing Make-Up Hydrogen Purity.
Increasing Recycle Gas Purity (Bleed, Treating)
Recycle Gas Rate.
Decreasing CHPS temperature.
Higher PH
2
Effects
Improves Product Properties (J et Smoke Point, Diesel
Cetane Number).
Increases Cycle Length.
Process variables:
Hydrogen Partial Pressure (pH
2
)
Process variables:
Process variables:
Hydrogen Partial Pressure (pH
Hydrogen Partial Pressure (pH
2 2
)
)
MAKE
MAKE
-
-
UP HYDROGEN QUALITY
UP HYDROGEN QUALITY
Parameter Hydrogen Specifications
Hydrogen Purity, Mole % 99.5(Min.)
CO + CO2, Mole 20 ppm (Max.)
Nitrogen, Mole 50 ppm (Max.)
Water, Mole 50 ppm (Max.)
Chlorine + Chlorides, Mole 1ppm (Max.)
Note: Co- more than 30ppm and reactor temp less than 200c, the
chances of nickel corbonyl formation is more. Which is highly toxic
Example: Effect of Increased Make-Up
Hydrogen Purity on Product Properties
and Cycle Length
Example: Effect of Increased Make
Example: Effect of Increased Make
-
-
Up
Up
Hydrogen Purity on Product Properties
Hydrogen Purity on Product Properties
and Cycle Length
and Cycle Length
SSOT Operation, System Pressure=169 kg/cm2
2 2 2
Make -Up Purity, % 85 96 99.9
Recycle Gas Purity, % 75 86.5 90
Hydrogen Partial Pressure,
kg/cm
2
G
125 136 140
Jet Smoke, mm 18 20 21
Diesel Cetane Number 50 53 55
Cycle Length, Months 14 24 29
Effects of High Recycle Gas rate (Gas/Oil Ratio)
Decreases Catalyst Fouling
Maintains High Hydrogen Partial Pressure in Reactors.
Providing a heat sink for high heat of reaction in the
bed.
Helps Distribution of Reactants Over the Catalyst
Bed.
Limits Bed Temperature Rise.
Increases Catalyst Activity
Minimizes "Overcracking" of Products by carrying
them out of the reactors before they can re-crack.
(Higher Liquid Yields)
Effects of High Recycle Gas rate (Gas/Oil Ratio)
Decreases Catalyst Fouling
Maintains High Hydrogen Partial Pressure in Reactors.
Providing a heat sink for high heat of reaction in the
bed.
Helps Distribution of Reactants Over the Catalyst
Bed.
Limits Bed Temperature Rise.
Increases Catalyst Activity
Minimizes "Overcracking" of Products by carrying
them out of the reactors before they can re-crack.
(Higher Liquid Yields)
Process variables: Recycle Gas Rate (Gas/Oil
Ratio)
Process variables
Process variables
:
:
Recycle Gas Rate (Gas/Oil
Recycle Gas Rate (Gas/Oil
Ratio)
Ratio)
Typical Design Guideline
Four to Five Times Chemical Hydrogen
Consumption
Recycle Gas Rate Should Be Maximized
Within Plant Mechanical Constraints.
minimum of 845 Nm3 reactor inlet gas per
m3 of fresh feed.
Typical Design Guideline
Four to Five Times Chemical Hydrogen
Consumption
Recycle Gas Rate Should Be Maximized
Within Plant Mechanical Constraints.
minimum of 845 Nm3 reactor inlet gas per
m3 of fresh feed.
Process variables: Recycle Gas Rate
(Gas/Oil Ratio)
Process variables
Process variables
:
:
Recycle Gas Rate
Recycle Gas Rate
(Gas/Oil Ratio)
(Gas/Oil Ratio)
Process variables
Process variables
-
-
Recycle Gas Purity
Recycle Gas Purity
Effects of Recycle Gas Purity:
1. Yields high hydrogen partial pressures.
2. Minimizes catalyst fouling.
Depends mainly on:
1. Make-up hydrogen purity.
2. The yield of methane in the reactors.
3. Gas bleed from CHPS.
4. CHPS inlet temperature.
ACTION TO BE TAKEN:
Taking a bleed, which results in an increase in the make-up hydrogen
rates, lowers the methane content of the recycle gas and improves hydrogen
rates, lowers the methane content of the recycle gas and improves hydrogen
partial pressure. Lowering the CHPS temperature will improve purity
because more light hydrocarbons will condense out of the recycle gas and
because less hydrogen dissolves at lower levels.
NOTE;
The design purity of the recycle gas is approximately 90.7 mole % H2 at
SOR and 85.6 mole % H2 at EOR. The recycle gas purity
1. Level Average Temperature (LAT)
2. Bed Average Temperature (BAT)
3. Catalyst Average Temperature (CAT)
Temperature Profile:
1. The LAT is the simple arithmetic average for a set of thermocouples at one
level in a catalyst bed.
2. The BAT is the simple arithmetic average of the bed inlet and outlet LATs.
3. The CAT is the weighted average of the BATs.
There are three types of profiles:
1. A flat temperature profile means the BATs are equal.
2. An ascending profile means that each successive BAT is higher than the bed
above.
3. A descending profile means that each successive BAT is lower than the bed
above. This profile is rarely used (or achievable).
Note: BAT, CAT, and temperature profiles are all used to monitor reactor
performance. The CAT determines how hard the catalyst is working and the
temperature profile describes how the work is distributed over the reactor.
1. Level Average Temperature (LAT)
2. Bed Average Temperature (BAT)
3. Catalyst Average Temperature (CAT)
Temperature Profile:
1. The LAT is the simple arithmetic average for a set of thermocouples at one
level in a catalyst bed.
2. The BAT is the simple arithmetic average of the bed inlet and outlet LATs.
3. The CAT is the weighted average of the BATs.
There are three types of profiles:
1. A flat temperature profile means the BATs are equal.
2. An ascending profile means that each successive BAT is higher than the bed
above.
3. A descending profile means that each successive BAT is lower than the bed
above. This profile is rarely used (or achievable).
Note: BAT, CAT, and temperature profiles are all used to monitor reactor
performance. The CAT determines how hard the catalyst is working and the
temperature profile describes how the work is distributed over the reactor.
Process variables; Reactor Temperature
Profile
Process variables
Process variables; ;
Reactor Temperature
Reactor Temperature
Profile
Profile
Catalyst Average Temperature (CAT )
Indicates How Hard Catalyst is Working.
Reactor Temperature Profile
Indicates How Work is Distributed Through the
Reactor.
Catalyst Average Temperature (CAT )
Indicates How Hard Catalyst is Working.
Reactor Temperature Profile
Indicates How Work is Distributed Through the
Reactor.
Process variables- catalyst
effects
Process variables
Process variables
-
-
catalyst
catalyst
effects
effects
Higher Catalyst Average Temperature Allows
Higher Feed Rates at Constant Product Qualities.
Better Product Qualities at Constant Feed Rate.
More Difficult Feeds (Higher S, N) at Constant Product
Qualities and Feed Rate.
But There is No Free Lunch
Higher CATs Increase Coking Rate.
Higher CATs Reduces catalyst Life due to increased
Fouling Rate.
Catalyst Average Temperature
Catalyst Average Temperature
Process variables
Process variables
-
-
catalyst life
catalyst life
The table below summarizes the effects of changing each
of the process variables on catalyst life.
Variable Change Effect on
Catalyst
Life
Feed Rate Increase Decrease
Conversion Increase Decrease
Hydrogen Partial
Pressure
Increase Increase
Make-Up Gas Purity Increase Increase
Reactor Pressure Increase Increase
Recycle Gas Rate Increase Increase
Recycle Gas Purity Increase Increase
WASH WATER INJ ECTION
WASH WATER INJ ECTION
Wash water is continuously injected into fin coolers to remove
ammonium salts.
Although incolloy tubes were selected for the reactor air
cooler, they may be subject to corrosion by deposition of
ammonium bisulfide (NH4HS) salts formed from the
combination of NH3 and H2S in the reactor and/or ammonium
chloride (NH4Cl) salts formed by the combination of NH3 and
HCl (from the chlorides in the feed).
The sublimation range for ammonium bisulfide is generally
about 66-93C. The sublimation range for ammonium chloride
begins at higher temperatures generally about 191-204C.
Therefore, NH4Cl will begin to sublime upstream of the
reactor air cooler.
Reactor air cooler corrosion is minimized by limiting the
chlorides in the feed in the make-up hydrogen, by use of high
alloy material, by balanced flow, and by continuous injection
of water at the air cooler inlet.
Process Variables have a significant impact on
Catalyst Life, Yields, and Product Properties
Understanding Process Variable Effects and
how these are related coupled with the
recognizing the constraints is critical to
maximizing Hydrocracker and Refinery
Profitability
Process Variables have a significant impact on
Catalyst Life, Yields, and Product Properties
Understanding Process Variable Effects and
how these are related coupled with the
recognizing the constraints is critical to
maximizing Hydrocracker and Refinery
Profitability
Summary of Process Variables
Summary of Process Variables
Summary of Process Variables
THANK YOU